Agent for the oxidative dyeing of hair, containing specific combinations of developers and couplers

ABSTRACT

An agent for oxidatively dyeing keratinous fibers includes in a cosmetic carrier: (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the physiologically acceptable salts thereof as developer; (B) at least one p-aminophenol derivative from the group comprising p-aminophenol, 4-amino-3-methylphenol, and/or the physiologically acceptable salts thereof as developer; (C) at least one m-diaminobenzene derivative from the group comprising 2-(2,4-diaminophenoxy)ethanol, 1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene, 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene, and/or one of the physiologically compatible salts thereof as coupler; and (D) at least one m-aminophenol derivative from the group 3-aminophenol, 5-amino-2-methylphenol and/or one of the physiologically acceptable salts thereof as coupler, wherein the molar ratio of all the developers of group (A) included in the agent to all the developers of group (B) included in the agent, i.e., the molar ratio (A)/(B), has a value of at least 1.2.

FIELD OF THE INVENTION

The present invention generally relates to an agent for oxidativelydyeing keratinous fibers, in particular human hair, which includesspecific combinations of oxidation dye precursors in certain molarratios relative to one another. The present invention also relates to amulticomponent packaging unit which includes the above-mentioned agent,and use of the agent for improving light fastness and wash fastness ofoxidative colorings.

BACKGROUND OF THE INVENTION

Changing the color of keratinous fibers, in particular hair, representsan important area of modern cosmetics. The appearance of the hair maythus be adapted to current fashion trends and to the person's individualpreferences. Various options are known to those skilled in the art forchanging the color of the hair. The hair color may be temporarilychanged by using direct dyes. In the process, dyes which are alreadyformed diffuse from the coloring agent into the hair fiber. Althoughcoloration using direct dyes involves little damage to the hair, it isdisadvantageous that the colorings obtained with direct dyes are notvery durable and wash out quickly.

If the user desires a long-lasting color result or a shade that islighter than his/her original hair color, oxidative color-changingagents are customarily used. For long-lasting, intense colorationshaving appropriate fastness properties, so-called oxidation dyes areused. Such coloring agents customarily include oxidation dye precursors,so-called developer components and coupler components, which form theactual dyes with one another under the influence of oxidizing agents.Oxidation dyes are characterized by long-lasting color results.

Extensive prior art already exists with regard to oxidative coloringagents. Considerable testing has been conducted, in particular foroptimizing the fastness properties of the colorings that are achievablewith these agents.

However, despite the large number of optimization tests already carriedout, there is still a need for improvement of the fastness properties ofoxidatively dyed keratin fibers, in particular when they are colored ina shade of red. In particular the wash fastness and light fastness ofshades of red, violet, and copper cannot yet be considered to beoptimal.

It is therefore desirable to provide oxidative coloring agents forachieving shades of red, violet, and copper having improved washfastness and improved light fastness.

The wash fastness of a color shade is understood to mean the change incolor of the hair strands colored with this shade under the influence ofmultiple hair washings. This change in color may involve a shift of thecolor toward another hue, or also lightening of the coloring. Bothchanges in color are equally undesirable to the user. Color shades withgood wash fastness experience little or no change in color, even afterrepeated hair washings. The hair washing may take place using a shampoo,a conditioning shampoo, or a conditioner.

The light fastness of a color shade is understood to mean the change incolor of the hair strands dyed with this shade under the influence ofsunlight (i.e., solar radiation or UV or UV/Vis radiation). Lighteningof the dyed hair is generally observed upon exposure to sunlight. Shadeshaving good light fastness experience little visible lightening of thecolor, even after multi-day exposure to sunlight.

Furthermore, other desirable features and characteristics of the presentinvention will become apparent from the subsequent detailed descriptionof the invention and the appended claims, taken in conjunction with thisbackground of the invention.

BRIEF SUMMARY OF THE INVENTION

The agent according to the invention includes4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole as the first developer, atleast one derivative of p-diaminophenol as the second developer, atleast one derivative of m-diaminobenzene as the first coupler, and atleast one derivative of m-aminophenol as the second coupler.

More particularly, an agent for oxidatively dyeing keratinous fibersincludes, in a cosmetic carrier,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of thephysiologically acceptable salts thereof as developer; at least onep-aminophenol derivative selected from p-aminophenol,4-amino-3-methylphenol, and/or the physiologically acceptable saltsthereof as developer; at least one m-diaminobenzene derivative selectedfrom 2-(2,4-diamino-phenoxy)ethanol,1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of thephysiologically acceptable salts thereof as coupler; and at least onem-aminophenol derivative selected from 3-aminophenol,5-amino-2-methylphenol, and/or one of the physiologically acceptablesalts thereof as coupler, wherein the molar ratio of all developers ofgroup (A) included in the agent to all developers of group (B) includedin the agent, i.e., the molar ratio (A)/(B), has a value of at least1.2.

DETAILED DESCRIPTION OF THE INVENTION

The following detailed description of the invention is merely exemplaryin nature and is not intended to limit the invention or the applicationand uses of the invention. Furthermore, there is no intention to bebound by any theory presented in the preceding background of theinvention or the following detailed description of the invention.

It has now surprisingly been found that colorings having excellent washfastness and light fastness may be produced on keratinous fibers whenthe latter are dyed with agents including specific combinations of twocertain oxidation dye precursors of the developer type and two certainoxidation dye precursors of the coupler type, and when the oxidation dyeprecursors of the developer type are used in certain molar ratiosrelative to one another.

The present invention firstly relates to an agent for oxidatively dyeingkeratinous fibers, which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.2.

Keratinous fibers, keratin-containing fibers, or keratin fibers areunderstood to mean fur, wool, feathers, and in particular human hair.Although the agents according to the invention are primarily suited forlightening and dyeing keratin fibers, use in other fields is alsopossible in principle.

The agents include the oxidation dye precursors essential to theinvention in each case in a cosmetic carrier, preferably in a suitableaqueous, alcoholic, or aqueous-alcoholic carrier. For purposes of theoxidative change in color, such carriers may be, for example, creams,emulsions, gels, or also surfactant-containing foaming solutions such asshampoos, foam aerosols, foam formulations, or other preparations thatare suitable for application to the hair. Agents for oxidatively dyeingkeratinous fibers are particularly preferably creams or emulsions.

The content of oxidation dye precursors of developer type (A) and (B) inthe agents, the content of oxidation dye precursors of coupler type (C)and (D) in the agents and the particular molar ratio of the developers(A)/(B) is characterizing for the agents according to the invention.

Within the meaning of the present invention, a developer is understoodto mean an oxidation dye precursor of the developer type. Within themeaning of the present invention, a coupler is understood to mean anoxidation dye precursor of the coupler type.

As the first oxidation dye precursor of developer type (A), the agentsaccording to the invention include4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of thephysiologically acceptable salts thereof4,5-Diamino-1-(2-hydroxyethyl)-1H-pyrazole is the compound of formula(I):

Preferred physiologically acceptable salts of4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole are in particular thehydrochlorides (monohydrochloride×HCI, or dihydrochloride×2 HCI), thesulfate (×H₂SO₄), and the hydrobromides (monohydrobromide×HBr, ordihydrobromide×2 HBr) of the compound.4,5-Diamino-1-(2-hydroxyethyl)-1H-pyrazole sulfate (formula (1a)) isvery particularly preferred:

As the second oxidation dye precursor of developer type (B), the agentsaccording to the invention at least one p-aminophenol derivative fromthe group comprising p-aminophenol itself, 4-amino-3-methylphenol,and/or the physiologically acceptable salts of these compounds.

p-Aminophenol is a compound of formula (II):

Preferred physiologically acceptable salts of p-aminophenol are inparticular the hydrochloride (monohydrochloride×HCI), the hemisulfate(×½ H₂SO₄), and the hydrobromide (monohydrobromide×HBr) of the compound.p-Aminophenol is particularly preferably used in the form of itshydrochloride (IIa):

4-Amino-3-methylphenol is the compound of formula (Ill):

Preferred physiologically acceptable salts of 4-amino-3-methylphenol arein particular the hydrochloride (monohydrochloride×HCI), the hemisulfate(×½ H₂SO₄), and the hydrobromide (monohydrobromide×HBr) of the compound.4-Amino-3-methylphenol hemisulfate (formula (IIIa)) is very particularlypreferred:

In the hemisulfate of 4-amino-3-methylphenol, in each case two moleculesof 4-amino-3-methylphenol having a protonated ammonium group are presentwhich are neutralized by a doubly negatively charged sulfate anion.Stoichiometrically, one-half of a sulfuric acid molecule is thus to beassociated with one molecule of 4-amino-3-methylphenol.

As the first oxidation dye precursor of coupler type (C), the agentsaccording to the invention include at least one m-diaminobenzenederivative from the group comprising 2-(2,4-diaminophenoxy)ethanol,1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,2,6-bis(2′-hydroxyethylamino)-1-methylbenzene, and/or one of thephysiologically acceptable salts of these m-diaminobenzene derivatives.

2-(2,4-Diaminophenoxy)ethanol is the compound of formula (IV):

Preferred physiologically acceptable salts of2-(2,4-diaminophenoxy)ethanol are in particular the hydrochlorides(monohydrochloride×HCI, or dihydrochloride×2 HCI), the sulfate (×H₂SO₄),and the hydrobromides (monohydrobromide×HBr, or dihydrobromide×2 HBr) ofthe compound. 2-(2,4-Diaminophenoxy)ethanol (dihydrochloride) (formula(IVa)) is very particularly preferred:

1-Methoxy-2-amino-4-(2′-hydroxyethylamino)benzene is the compound offormula (V):

Preferred physiologically acceptable salts of1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene are in particular thehydrochlorides (monohydrochloride×HCI, or dihydrochloride×2 HCI), thesulfate (×H₂SO₄), and the hydrobromides (monohydrobromide×HBr, ordihydrobromide×2 HBr) of the compound.1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene is particularlypreferably used not in the salt form, but, rather, in the form of thefree compound (i.e., as the compound of formula ((V)).

2,6-bis(2′-Hydroxyethylamino)-1-methylbenzene is the compound of formula(VI).

Preferred physiologically acceptable salts of2,6-bis(2′-hydroxyethylamino)-1-methylbenzene are in particular thehydrochlorides (monohydrochloride×HCI, or dihydrochloride×2 HCI), thesulfate (×H₂SO₄), and the hydrobromides (monohydrobromide×HBr, ordihydrobromide×2 HBr) of the compound.2,6-bis(2′-Hydroxyethylamino)-1-methylbenzene is particularly preferablyused, not in the salt form, but, rather, in the form of the freecompound (i.e., as the compound of formula (VI)).

As the second oxidation dye precursor of coupler type (D), the agentsaccording to the invention include at least one m-aminophenol derivativefrom the group comprising 3-aminophenol itself, 5-amino-2-methylphenol,and/or one of the physiologically acceptable salts of thesem-aminophenol derivatives.

3-Aminophenol is the compound of formula (VII):

Preferred physiologically acceptable salts of 3-aminophenol are inparticular the hydrochlorides (monohydrochloride×HCI, ordihydrochloride×2 HCI), the sulfate (×H₂SO₄), and the hydrobromides(monohydrobromide×HBr, or dihydrobromide×2 HBr) of the compound.3-Aminophenol is particularly preferably used not in the salt form, but,rather, in the form of the free compound (i.e., as the compound offormula (VII)).

5-Amino-2-methylphenol is the compound of formula (VIII). An alternativename for 5-amino-2-methylphenol is 4-amino-2-hydroxytoluene.

Preferred physiologically acceptable salts of 5-amino-2-methylphenol arein particular the hydrochlorides (monohydrochloride×HCI, ordihydrochloride×2 HCI), the sulfate (×H₂SO₄), and the hydrobromides(monohydrobromide×HBr, or dihydrobromide×2 HBr) of the compound.5-Amino-2-methylphenol is particularly preferably used not in the saltform, but, rather, in the form of the free compound (i.e., as thecompound of formula (VIII)).

In the course of the studies leading to the present invention, it hasbeen found that using a combination of the four different oxidation dyeprecursors (A), (B), (C), and (D), compared to using only threeoxidation dye precursors (for example, (A), (C), and (D) or (A), (B),and (C)) in oxidative coloring agents results in improved wash fastness,and at the same time also improved light fastness, when the oxidationdyes of developer type (A) and (B) are used in a certain molar ratio(A)/(B) relative to one another.

The molar mass (units: g/mol) of a compound is defined as the mass(units: g) per substance quantity (units: mol).

During the oxidative dyeing process, in each case one molecule of anoxidation dye precursor of the developer type reacts with one or moremolecules of the oxidation dye precursor of the coupler type. It hasbeen found that high color intensities and good fastness properties maybe achieved when the substance quantities of the dye precursors reactingwith one another (i.e., their molar quantities) are coordinatedparticularly well with one another.

The substance quantity is understood to mean the quantity of a materialportion, based on the number of particles respectively included therein.The substance quantity is expressed in the base units of moles (mol ormmol).

The molar quantity of the oxidation dye precursor included in a coloringagent may be obtained by dividing the quantity used by its molarquantity. Example:

100 g of a color cream includes

(A) 4.80 g of 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole sulfate.

Molar mass of 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole sulfate=240.23g/mol.

The molar quantity of the 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazolesulfate included in the agent (100 g) is (4.80 g/[240.23 g/mol)=0.020mol (corresponds to 20.0 mmol).

It has now been found that the formulation of shades in the red, copper,and violet range is possible when a deficit of developers of group (B)is admixed with the developers of group (A). In this way, the lightfastness and wash fastness of the colorings which are achievable withthese shades may also surprisingly be improved.

Advantageous effects on the light fastness and wash fastness of thecolorings which are achievable with these agents may thus be observed inparticular when the developers from group (A) are used in the agents ina molar excess with respect to the developers from group (B), i.e., whenthe molar ratio (A)/(B) has a value greater than 1.2.

The basis for calculating the molar ratio (A)/(B) is the total molarquantity of all developers of group (A) included in the agent (i.e., themolar quantity of 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole plus themolar quantities of its salts), which is set in a relation with thetotal molar quantity of all developers of group (B) included in theagent (i.e., the molar quantity of p-aminophenol and4-amino-3-methylphenol plus the molar quantities of its salts). At leastone compound from the group of developers (B) comprising p-aminophenolor 4-amino-3-methylphenol or the salts thereof must be included.

A very particularly preferred agent for oxidatively dyeing keratinousfibers is characterized in that the molar ratio of all developers ofgroup (A) included in the agent to all developers of group (B) includedin the agent, i.e., the molar ratio (A)/(B), has a value of at least1.4, preferably at least 1.6, more preferably at least 1.8, even morepreferably at least 1.6, and particularly preferably at least 1.9.

It has been possible to achieve the best wash fastness and the bestlight fastness when the agents according to the invention included thedevelopers of group (A) in a total molar quantity approximately twicethat of group (B).

The oxidative coloring agents which include the developers from group(A) and the developers from group (B) in a molar ratio of 1.8 to 2.5have the best fastness properties. However, if the molar ratio of(A)/(B) further increases to values greater than 4.5, there is atendency once again toward degradation of the wash fastness and thelight fastness of the colorings obtained with these agents. For thisreason, it is advantageous for the molar ratio (A)/(B) not to exceedvalues of 4.5.

A very particularly preferred agent for oxidatively dyeing keratinousfibers is characterized in that the molar ratio of all developers ofgroup (A) included in the agent to all developers of group (B) includedin the agent, i.e., the molar ratio (A)/(B), has a value of 4.5 maximum,preferably 4.0 maximum, more preferably 3.5 maximum, even morepreferably 3.0 maximum, and particularly preferably 2.5 maximum.

Example

100 g of a color cream includes

-   -   (A) 4.80 g of 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole        sulfate.        The molar quantity of the        4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole sulfate included in        the agent (100 g) is (4.80 g/[240.23 g/mol])=0.020 mol        (corresponding to 20.0 mmol)    -   (B) 1.72 g 4-amino-3-methylphenol (hemisulfate)        The molar quantity of the 4-amino-3-methylphenol (hemisulfate)        included in the agent (100 g) is        (1.72 g/[172.18 g/mol])=0.010 mol (corresponding to 10.0 mmol).        The molar ratio (A)/(B) has a value of (0.020 mol)/(0.010        mol)=2.

Example

100 g of a color cream includes

-   -   (A) 4.80 g of 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole        sulfate.        The molar quantity of the        4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole sulfate included in        the agent (100 g) is (4.80 g/[240.23 g/mol])=0.020 mol        (corresponding to 20.0 mmol)    -   (B) 1.46 g p-aminophenol (hydrochloride)        The molar quantity of the p-aminophenol (hydrochloride) included        in the agent (100 g) is (1.46 g/[145.59 g/mol])=0.010 mol        (corresponding to 10.0 mmol)        The molar ratio (A)/(B) has a value of (0.020 mol)/(0.010        mol)=2.

As the second oxidation dye precursor of developer type (B), the agentsaccording to the invention include at least one p-diaminophenolderivative from the group comprising p-aminophenol,4-amino-3-methyl-phenol, and/or the physiologically acceptable salts ofthese compounds.

Both developers from group (B) have proven to be very particularlysuited for use in combination with the further oxidation dye precursors(A), (C), and (D) according to the invention.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is thereforecharacterized in that it includes

-   -   (B) 4-amino-3-methylphenol and/or one of the physiologically        acceptable salts thereof as developer.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is thereforecharacterized in that it includes

-   -   (B) p-aminophenol and/or one of the physiologically acceptable        salts thereof as developer.

As the first oxidation dye precursor of coupler type (C), the agentsaccording to the invention include at least one m-diaminobenzenederivative from the group comprising 2-(2,4-diaminophenoxy)ethanol,1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,2,6-bis(2′-hydroxyethylamino)-1-methylbenzene, and/or one of thephysiologically acceptable salts of these m-diaminobenzene derivatives.

With regard to improvement of the fastness properties,2-(2,4-diaminophenoxy)ethanol and2,6-bis(2′-hydroxyethylamino)-1-methylbenzene in particular have provento be very particularly suited.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is thereforecharacterized in that it includes

-   -   (C) 2-(2,4-diaminophenoxy)ethanol and/or one of the        physiologically acceptable salts thereof as coupler.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is thereforecharacterized in that it includes

-   -   (C) 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene and/or one of        the physiologically acceptable salts thereof as coupler.

As the second oxidation dye precursor of coupler type (D), the agentsaccording to the invention include at least one m-aminophenol derivativefrom the group comprising 3-aminophenol, 5-amino-2-methylphenol, and/orone of the physiologically acceptable salts of these m-aminophenolderivatives.

The coupler 5-amino-2-methylphenol from group (D) has proven to be verypreferably suitable with regard to optimizing the fastness properties.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is thereforecharacterized in that it includes

-   -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) 4-amino-3-methylphenol and/or one of the physiologically        acceptable salts thereof as developer,    -   (C) 2-(2,4-diaminophenoxy)ethanol and/or one of the        physiologically acceptable salts thereof as coupler,    -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.2.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) p-aminophenol and/or one of the physiologically acceptable        salts thereof as developer,    -   (C) 2-(2,4-diaminophenoxy)ethanol and/or one of the        physiologically acceptable salts thereof as coupler,    -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.2.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) 4-amino-3-methylphenol and/or one of the physiologically        acceptable salts thereof as developer,    -   (C) 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene and/or one of        the physiologically acceptable salts thereof as coupler,    -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.2.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) p-aminophenol and/or one of the physiologically acceptable        salts thereof as developer,    -   (C) 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene and/or one of        the physiologically acceptable salts thereof as coupler,    -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.2.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.4.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.6.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.8.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.9.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of 1.4 to 4.5.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of 1.6 to 4.0.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of 1.8 to 3.5.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) at least one m-diaminobenzene derivative from the group        comprising 2-(2,4-diamino-phenoxy)ethanol,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        2,6-bis(2′-hydroxy-ethylamino)-1-methylbenzene, and/or one of        the physiologically acceptable salts thereof as coupler, and    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of 1.9 to 2.5.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) 4-amino-3-methylphenol and/or one of the physiologically        acceptable salts thereof as developer,    -   (C) 2-(2,4-diaminophenoxy)ethanol and/or one of the        physiologically acceptable salts thereof as coupler,    -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of 1.9 to 2.5.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) p-aminophenol and/or one of the physiologically acceptable        salts thereof as developer,    -   (C) 2-(2,4-diaminophenoxy)ethanol and/or one of the        physiologically acceptable salts thereof as coupler,    -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of 1.9 to 2.5.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) 4-amino-3-methylphenol and/or one of the physiologically        acceptable salts thereof as developer,    -   (C) 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene and/or one of        the physiologically acceptable salts thereof as coupler,    -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of 1.9 to 2.5.

Accordingly, an agent for oxidatively dyeing keratinous fibers isparticularly preferred which includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) p-aminophenol and/or one of the physiologically acceptable        salts thereof as developer,    -   (C) 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene and/or one of        the physiologically acceptable salts thereof as coupler,    -   (D) 5-amino-2-methylphenol and/or one of the physiologically        acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of 1.9 to 2.5.

In another embodiment, it is likewise preferred when the agentsaccording to the invention include at least two oxidation dye precursorsof the coupler type from group (C).

An agent for oxidatively dyeing keratinous fibers is also preferredwhich includes in a cosmetic carrier

-   -   (A) 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of the        physiologically acceptable salts thereof as developer,    -   (B) at least one p-aminophenol derivative from the group        comprising p-aminophenol, 4-amino-3-methylphenol, and/or the        physiologically acceptable salts thereof as developer,    -   (C) 2-(2,4-diaminophenoxy)ethanol and        2,6-bis(2′-hydroxyethylamino)-1-methylbenzene as coupler,    -   (D) at least one m-aminophenol derivative from the group        comprising 3-aminophenol, 5-amino-2-methylphenol, and/or one of        the physiologically acceptable salts thereof as coupler,    -   wherein    -   the molar ratio of all developers of group (A) included in the        agent to all developers of group (B) included in the agent,        i.e., the molar ratio (A)/(B), has a value of at least 1.2.

In tests conducted for the present invention, it was also found that themolar ratio of the couplers from groups (C) and (D) relative to oneanother may also have a great influence on the fastness properties. Thebest wash fastness was observed when the couplers from group (C) and thecouplers from group (D) were used in approximately equimolar quantities,i.e., when the ratio (C)/(D) had a value equal or close to 1. Oxidativecoloring agents including the couplers from groups (C) and (D) in amolar ratio of approximately 1 also showed the best light fastness.

The basis for calculating the molar ratio (C)/(D) is the total molarquantity of all couplers of group (C) included in the agent (i.e., themolar quantity of 2-(2,4-diaminophenoxy)ethanol,1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene, and2,6-bis(2′-hydroxyethylamino)-1-methylbenzene plus the molar quantitiesof their salts), which is set in a relation with the total molarquantity of all couplers of group (D) included in the agent (i.e., thesum of the molar quantities of 3-aminophenol and 5-amino-2-methylphenolplus the molar quantities of their salts). Once again, in each case atleast one coupler from groups (C) and (D) must be included in the agentaccording to the invention.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is characterizedin that the molar ratio of all couplers of group (C) included in theagent to all couplers of group (D) included in the agent, i.e., themolar ratio (C)/(D), has a value of at least 0.5, preferably at least0.6, more preferably at least 0.7, and particularly preferably at least0.8.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is furthercharacterized in that the molar ratio of all couplers of group (C)included in the agent to all couplers of group (D) included in theagent, i.e., the molar ratio (C)/(D), has a value of 1.5 maximum,preferably 1.4 maximum, more preferably 1.3 maximum, and particularlypreferably 1.2 maximum.

For application-related reasons as well as toxicological reasons, thecouplers are used in a slight molar excess in the ratio with respect tothe developers. The best results have been obtained when the molar ratioof all developers of groups (A) and (B) included in the agent to allcouplers of groups (C) and (D) included in the agent, i.e., the molarratio [(A)+(B)]/[(C)+(D)], has a value of approximately 0.75, whichmeans that for 3 molar portions of developers [(A)+(B)], approximately 4molar portions of couplers [(C)+(D)] are used. Similarly good resultshave also been obtained within a variation range; i.e., the fastnessvalues were excellent even when the molar ratio [(A)+(B)]/[(C)+(D)] hadvalues between 0.65 and 0.80. In addition, it was possible to avoid skinirritations while maintaining these molar ratios.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is thereforecharacterized in that the molar ratio of all developers of groups (A)and (B) included in the agent to all couplers of groups (C) and (D)included in the agent, i.e., the molar ratio [(A)+(B)]/[(C)+(D)], has avalue of at least 0.4, preferably at least 0.5, more preferably at least0.6, and particularly preferably at least 0.65.

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is furthercharacterized in that the molar ratio of all developers of groups (A)and (B) included in the agent to all couplers of groups (C) and (D)included in the agent, i.e., the molar ratio [(A)+(B)]/[(C)+(D)], has avalue of 0.95 maximum, preferably 0.90 maximum, more preferably 0.85maximum, and particularly preferably 0.80 maximum.

The basis for calculating the molar ratio [(A)+(B)]/[(C)+(D)] isanalogous to the above-mentioned calculations of the total molarquantity of all developers from groups (A) and (B) included in theagent, which are set in a relation with the total molar quantity of allcouplers from groups (C) and (D) included in the agent.

The ready-to-apply oxidative coloring agent is prepared shortly beforeapplication by mixing two (or more) different components.

The first component is color preparation (K1), which is preferably setalkaline, and which includes the oxidation dye precursors (A), (B), (C),and (D) (and optionally even further additional oxidation dye precursorsand/or further direct dyes). This color preparation is mixed with anoxidizing agent preparation (K2) prior to application. For stabilityreasons, the oxidizing agent preparation (K2) is preferably set to anacidic pH, and includes the oxidizing agent. The oxidizing agent isusually hydrogen peroxide, which is used in the form of its aqueoussolution.

The components (K1) and (K2) may be combined with one another indifferent weight ratios from 1:3 to 3:1, resulting in the ready-to-applyoxidative coloring agent. The components (K1) and (K2) are preferablymixed together in a quantity ratio of 1:1.

All oxidation dye precursors are included in color preparation (K1);therefore, all statements concerning weight quantities, weight ratios,molar quantities, molar ratios, and molalities of the oxidation dyeprecursors refer to the overall quantity of color preparation (K1).

It has now been found to be advantageous when the agents according tothe invention for oxidatively dyeing keratin fibers preferably includethe developers of group (A) in a certain overall molality.

The overall molality is understood to mean the total molar quantity ofall developers from group (A) included in the oxidative coloring agent;this overall molality refers to the total molar quantity of thedevelopers (A) in the total weight of color preparation (K1) (units: moldeveloper (A) per kg of color preparation (K1)).

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is thereforecharacterized in that it includes the developer(s) of group (A) in anoverall molality of 0.10 to 0.50 mol/kg, preferably 0.15 to 0.45 mol/kg,and particularly preferably 0.20 to 0.40 mol/kg, based on the totalweight of the agent.

Since all the oxidation dye precursors are present in color preparation(K1), the total weight of the above-mentioned agent is understood tomean the total weight of color preparation (K1).

Color preparation (K1), which particularly preferably includes thedevelopers of group (A) in an overall molality of 0.20 to 0.40 mol/kg,is then mixed with oxidizing agent preparation (K2) prior toapplication. For a mixing ratio (K1)/(K2) of 1:1, the resultingready-to-apply oxidative coloring agent consequently includes thedevelopers from group (A) in an overall molality of 0.10 to 0.20 mol/kg.

The couplers of groups (C) and (D) are likewise particularly preferablyincluded in certain overall molalities in the agent according to theinvention. Colorings with excellent fastness properties have beenobtained when the couplers are used within these preferred quantityranges.

The overall molality is understood to mean the total molar quantity ofall couplers from groups (C) and (D) included in the oxidative coloringagent; the overall molality refers to the total molar quantity ofcouplers (C) and (D) in the total weight of color preparation (K1)(units: mol couplers [(C)+(D)] per kg of color preparation (K1)).

In another very particularly preferred embodiment, an agent according tothe invention for oxidatively dyeing keratinous fibers is thereforecharacterized in that it includes the couplers of groups (C) and (D) inan overall molality of 0.10 to 1.00 mol/kg, preferably 0.20 to 0.90mol/kg, more preferably 0.30 to 0.80 mol/kg, and particularly preferably0.40 to 0.70 mol/kg, based on the total weight of the agent.

Since all the oxidation dye precursors are present in color preparation(K1), the total weight of the above-mentioned agent is understood tomean the total weight of color preparation (K1).

For further shading, the agents according to the invention (i.e., colorpreparation (K1)) may additionally include even further oxidation dyeprecursors of the developer type and/or of the coupler type which aredifferent from the developers and couplers from groups (A), (B), (C),and (D).

Preferred additional oxidation dye precursors of the developer type maybe selected from the group comprising p-phenylenediamine,2-(1,2-dihydroxyethyl)-p-phenylenediamine,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,2-(2,5-diaminophenyl)ethanol, 2-methoxymethyl-p-phenylenediamine,N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine,N,N′-bis-(2-hydroxyethyl)-N,N′-bis-(4-aminophenyl)-1,3-diaminopropan-2-ol,bis-(2-hydroxy-5-aminophenyl)methane,1,3-bis-(2,5-diaminophenoxy)propan-2-ol,N,N′-bis-(4-aminophenyl)-1,4-diazacycloheptane, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, p-aminophenol,4-amino-3-methylphenol, 4-amino-2-aminomethylphenol,2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, and physiologically acceptable saltsthereof.

Coupler components which may additionally be included are preferablyselected from one of the following classes: o-aminophenol,m-diaminobenzene, o-diaminobenzene, and/or the derivatives thereof;naphthalene derivatives including at least one hydroxy group;trihydroxybenzene derivatives; pyridine derivatives; pyrimidinederivatives; indole derivatives, and indoline derivatives; pyrazolonederivatives (1-phenyl-3-methylpyrazol-5-one, for example); morpholinederivatives (6-hydroxybenzomorpholine or 6-aminobenzomorpholine, forexample); quinoxaline derivatives(6-methyl-1,2,3,4-tetrahydroquinoxaline, for example), and mixtures oftwo or more compounds of one or more of these classes.

Preferred additional m-aminophenol coupler components are selected fromat least one compound from the group comprising resorcinol,2-methylresorcinol, 4-chlororesorcinol, N-cyclopentyl-3-aminophenol,3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol,2,6-dimethyl-3-aminophenol,3-trifluoroacetylamino-2-chloro-6-methylphenol,5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-(2′-hydroxyethyl)amino-2-methylphenol, 3-diethylaminophenol,N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)benzene,3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol, and thephysiologically acceptable salts thereof. Preferred additionalm-diaminobenzene coupler components are selected from at least onecompound from the group comprising m-phenylenediamine,1,3-bis(2,4-diaminophenoxy)propane, 1,3-bis(2,4-diaminophenyl)propane,2-({3-[(2-hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol,2-({3-[(2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol,2-({3-[(2-hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol,2-[3-morpholin-4-ylphenyl)amino]ethanol,3-amino-4-(2-methoxyethoxy)-5-methylphenylamine,1-amino-3-bis-(2′-hydroxyethyl)aminobenzene, and the physiologicallyacceptable salts thereof. Preferred o-diaminobenzene coupler componentsare selected from at least one compound from the group comprising3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and thephysiologically acceptable salts thereof. Preferred naphthalenederivatives including at least one hydroxy group are selected from atleast one compound of the group comprising 1-naphthol,2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol,2-hydroxyethyl-1-naphthol, 1,3-dihydroxynaphthalene,1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene,2,7-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene. Preferredtrihydroxybenzenes and the derivatives thereof are selected from atleast one compound of the group comprising pyrogallol and1,2,4-trihydroxybenzene. Preferred pyridine derivatives are selectedfrom at least one compound of the group comprising2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine,2-amino-5-chloro-3-hydroxypyridine,3-amino-2-methylamino-6-methoxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine,2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine,3,5-diamino-2,6-dimethoxypyridine, 3,4-diaminopyridine,2-(2-methoxyethyl)amino-3-amino-6-methoxypyridine,2-(4′-methoxyphenyl)amino-3-aminopyridine, and the physiologicallyacceptable salts thereof. Preferred pyrimidine derivatives are selectedfrom at least one compound of the group comprising4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine,2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, and4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptablesalts thereof. Preferred indole derivatives are selected from at leastone compound of the group comprising 4-hydroxyindole, 6-hydroxyindole,and 7-hydroxyindole and the physiologically acceptable salts thereof.Preferred indoline derivatives are selected from at least one compoundof the group comprising 4-hydroxyindoline, 6-hydroxyindoline, and7-hydroxyindoline and the physiologically acceptable salts thereof.

Additional coupler components particularly preferred according to theinvention are selected from among resorcinol, 2-methylresorcinol,4-chlororesorcinol, 3-amino-2-chloro-6-methylphenol,2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol,5-(2-hydroxyethyl)amino-2-methylphenol, 2,4-dichloro-3-aminophenol,2-aminophenol, 3-phenylenediamine, 1,3-bis(2,4-diaminophenoxy)propane,1,3-bis(2,4-diaminophenyl)propane,2-({3-[(2-hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol,2-({3-[(2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol,2-({3-[(2-hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol,2[3-morpholin-4-yl-phenyl)amino]ethanol,3-amino-4-(2-methoxyethoxy)-5-methylphenylamine,1-amino-3-bis-(2-hydroxyethyl)aminobenzene, 2,4-trihydroxybenzene,2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine,1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole,7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline,7-hydroxyindoline, or mixtures of these compounds or the physiologicallyacceptable salts thereof. Very particularly preferred are5-amino-2-methylphenol, 3-aminophenol,1,3-bis(2,4-diaminophenoxy)propane, 2-amino-3-hydroxypyridine, and1-naphthol, and one of the physiologically acceptable salts thereof.

In addition, the agents according to the invention (i.e., colorpreparation (K1)) may likewise include at least one direct dye from thegroup comprising the anionic, nonionic, and/or cationic dyes.

Particularly preferred are one or more nonionic direct dyes from thegroup comprising HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HCYellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 7,HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HCBlue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, DisperseViolet 4, Disperse Black 9, 1,4-diamino-2-nitrobenzene,2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)amino-2-nitrobenzene,3-nitro-4-(2-hydroxyethyl)aminophenol,2-(2-hydroxyethyl)amino-4,6-dinitrophenol,4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene,4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,4-[(3-hydroxypropyl)amino]-3-nitrophenol, 4-nitro-o-phenylenediamine,6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone,picramic acid and the salts thereof, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitro benzoic acid, and2-chloro-6-ethylamino-4-nitrophenol.

In another particularly preferred embodiment, the agent according to theinvention is characterized in that it additionally includes one or morenonionic direct dyes from the group comprising HC Yellow 2, HC Yellow 4,HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3,HC Red 1, HC Red 3, HC Red 7, HC Red 10, HC Red 11, HC Red 13, HC RedBN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1,Disperse Violet 1, Disperse Violet 4, Disperse Black 9,1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol,1,4-bis-(2-hydroxyethyl)amino-2-nitrobenzene,3-nitro-4-(2-hydroxyethyl)aminophenol,2-(2-hydroxyethyl)amino-4,6-dinitrophenol,4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene,4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,4-[(3-hydroxypropyl)amino]-3-nitrophenol, 4-nitro-o-phenylenediamine,6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone,picramic acid and the salts thereof, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitro benzoic acid, and2-chloro-6-ethylamino-4-nitrophenol.

In addition, anionic direct dyes may also be included which are known bythe international designations or trade names Acid Yellow 1, Yellow 10,Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52,Pigment Red 57:1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black1, Acid Black 52, bromophenol blue, and tetrabromophenol blue.

Suitable cationic direct dyes are cationic triphenylmethane dyes, forexample Basic Blue 7, Basic Blue 26, Basic Violet 2, and Basic Violet14, aromatic systems substituted with a quaternary nitrogen group, forexample Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16,and Basic Brown 17, cationic anthraquinone dyes such as HC Blue 16(Bluequat B), and direct dyes which include a heterocycle having atleast one quaternary nitrogen atom, in particular Basic Yellow 87, BasicOrange 31, and Basic Red 51. The cationic direct dyes, which aremarketed under the trademark Arianor, are likewise suitable cationicdirect dyes according to the invention.

The additional oxidation dye precursors, i.e., developer components andcoupler components, which are different from the compounds of groups(A), (B), (C), and (D), and the optionally additionally included directdyes may be used, for example, in a quantity of 0.0001 to 5.0% byweight, preferably 0.001 to 3.5% by weight, in each case based on thetotal weight of color preparation (K1).

Shortly before application, the agent according to the invention(corresponding to color preparation (K1)) is mixed with an oxidizingagent preparation. The ready-to-apply oxidative coloring agent isobtained in this way.

For sufficient swelling of the keratin fibers, the ready-to-applyoxidative coloring agent is preferably set to an alkaline pH. The dyeingprocesses on keratin fibers also customarily proceed in an alkalineenvironment. However, to protect the keratin fibers and also the skin tothe greatest extent possible, setting a pH that is too high is notdesirable. It is therefore preferred when the pH of the ready-to-applyagent has a value of 8.0 to 10.5, more preferably 8.7 to 10.3, even morepreferably 9.0 to 10.2, and particularly preferably 9.2 to 10.1. Thestated pH values are values that have been measured at a temperature of22° C. with a glass electrode.

The alkalizing agents that are usable according to the invention forsetting the preferred pH may be selected from ammonia, alkanolamines,basic amino acids, and inorganic alkalizing agents such as earthalkaline or alkali metal hydroxides, earth alkaline or alkali metalmetasilicates, earth alkaline or alkali metal phosphates, and earthalkaline or alkali metal hydrogen phosphates. Preferred inorganicalkalizing agents are sodium hydroxide, potassium hydroxide, sodiumsilicate, and sodium metasilicate. Organic alkalizing agents that areusable according to the invention are preferably selected frommonoethanolamine, 2-amino-2-methylpropanol, and triethanolamine. Thebasic amino acids that are usable as alkalizing agents according to theinvention are preferably selected from the group comprising arginine,lysine, ornithine, and histidine, particularly preferably arginine.However, in the testing for the present invention, it has been foundthat further agents preferred according to the invention arecharacterized in that they additionally include an organic alkalizingagent. One embodiment of the first subject matter of the invention ischaracterized in that the agent additionally includes at least onealkalizing agent that is selected from the group comprising ammonia,alkanolamines, and basic amino acids, in particular ammonia,monoethanolamine, and arginine or the acceptable salts thereof. Thealkalizing agent(s) together with the oxidation dye precursors is/arepreferably provided in color preparation (K1).

A second subject matter of the present invention relates to amulticomponent packaging unit (kit-of-parts) for oxidatively dyeingkeratinous fibers, comprising two preparations (K1) and (K2) that areseparately packaged, wherein

preparation (K1) is an agent of the first subject matter of theinvention,

preparation (K2) includes hydrogen peroxide in an aqueous cosmeticcarrier, and

the mixture of (K1) and (K2) has a pH of 8.0 to 10.5, preferably 8.7 to10.3, more preferably 9.0 to 10.2, and particularly preferably 9.2 to10.1.

In one preferred embodiment, hydrogen peroxide itself is used as theaqueous solution in oxidizing agent preparation (K2). The concentrationof a hydrogen peroxide solution in color preparation (K2) is determinedon the one hand by the regulatory requirements, and on the other hand bythe desired effect; 6 to 12% by weight solutions in water are preferablyused. Preparations (K2) preferred according to the invention arecharacterized in that they include 5 to 20% by weight, preferably 1 to12.5% by weight, particularly preferably 2.5 to 10% by weight, and inparticular 3 to 6% by weight, of hydrogen peroxide, in each case basedon the total weight of oxidizing agent preparation (K2).

Color preparation (K1) and/or oxidizing agent preparation (K2) mayinclude further bleach enhancers for increasing the lightening effect,for example tetraacetylethylenediamine (TAED),1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),tetraacetylglycoluril (TAGU), N-nonanoyl succinimide (NOSI), n-nonanoylor isononanoyloxybenzenesulfonate (n- or iso-NOBS), phthalic acidanhydride, triacetin, ethylene glycol diacetate, and2,5-diacetoxy-2,5-dihydrofuran, as well as carbonate salts or hydrogencarbonate salts, in particular ammonium hydrogen carbonate, ammoniumcarbonate, sodium hydrogen carbonate, disodium carbonate, potassiumhydrogen carbonate, dipotassium carbonate, and calcium carbonate, andnitrogen-containing heterocyclic bleach enhancers, such as4-acetyl-1-methylpyridinium-p-toluenesulfonate,2-acetyl-1-methylpyridinium-p-toluenesulfonate, andN-methyl-3,4-dihydroisoquinolinium-p-toluenesulfonate.

For further increasing the lightening, at least one SiO₂ compound suchas silicic acid or silicates, in particular water glasses, mayadditionally be added to color preparation (K1) and/or oxidizing agentpreparation (K2). The SiO₂ compound may be included in color preparation(K1) and/or in oxidizing agent preparation (K2). It may be preferredaccording to the invention to use the SiO₂ compounds in quantities of0.05% by weight to 15% by weight, particularly preferably in quantitiesof 0.15% by weight to 10% by weight, and very particularly preferably inquantities of 0.2% by weight to 5% by weight, in each case based on thetotal weight of color preparation (K1) or the total weight of oxidizingagent preparation (K2). The stated quantities in each case represent thecontent of the SiO₂ compounds in the agents (not including their waterfraction).

The oxidative color change agents (i.e., color preparation (K1) and/oroxidizing agent preparation (K2)) may also include further activesubstances, auxiliary substances, and additives in order to improve thecoloring or lightening power and to set further desired properties inthe agent.

The ready-to-apply coloring agents are preferably provided as a liquidpreparation, and optionally a further surface-active substance isadditionally added to the agents; depending on the field of application,such surface-active substances are referred to as surfactants or asemulsifiers. They are preferably selected from anionic, zwitterionic,amphoteric, and nonionic surfactants and emulsifiers.

Agents which are suitable according to the invention are characterizedin that the agent additionally includes at least one anionic surfactant.Preferred anionic surfactants are fatty acids, alkyl sulfates, alkylether sulfates, and ether carboxylic acids including 10 to 20 C atoms inthe alkyl group and up to 16 glycol ether groups in the molecule.

Agents which are suitable according to the invention are characterizedin that the agent additionally includes at least one zwitterionicsurfactant. Preferred zwitterionic surfactants are betaines,N-alkyl-N,N-dimethylammonium glycinates,N-acylaminopropyl-N,N-dimethylammonium glycinates, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines. One preferredzwitterionic surfactant is known by the INCI name CocamidopropylBetaine.

Agents which are suitable according to the invention are characterizedin that the agent additionally includes at least one amphotericsurfactant. Preferred amphoteric surfactants are N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionicacids, and alkylaminoacetic acids. Particularly preferred amphotericsurfactants are N-cocoalkylamino propionate, cocoacylaminoethylaminopropionate, and C₁₂-C₁₈ acyl sarcosine.

In addition, it has proven to be advantageous when the agents includefurther, noniogenic surface-active substances. Preferred nonionicsurfactants are alkyl polyglycosides and alkylene oxide additionproducts with fatty alcohols and fatty acids in each case including 2 to30 mol ethylene oxide per mol fatty alcohol or fatty acid. Preparationshaving excellent properties are likewise obtained when they includefatty acid esters of ethoxylated glycerin as nonionic surfactants.

The nonionic, zwitterionic, or amphoteric surfactants are used inproportions of 0.1 to 45% by weight, preferably 1 to 30% by weight, andvery particularly preferably 1 to 15% by weight, based on the totalquantity of the ready-to-apply agents.

The ready-to-apply color-changing agents may also include at least onethickener. In principle, there are no limitations with regard to thesethickeners. Organic as well as strictly inorganic thickeners may beused.

Suitable thickeners are anionic synthetic polymers, cationic syntheticpolymers, naturally occurring thickeners, such as nonionic guar gums,scleroglucan gums, or xanthan gums, gum arabic, gum ghatti, karaya gum,gum tragacanth, carrageenan gum, agar-agar, locust bean gum, pectins,alginates, starch fractions, and derivatives such as amylose,amylopectin, and dextrins, and cellulose derivatives such asmethylcellulose, carboxyalkyl celluloses, and hydroxyalkyl celluloses,nonionic synthetic polymers such as polyvinyl alcohol orpolyvinylpyrrolidinone, and inorganic thickeners, in particularphyllosilicates such as bentonite, in particular smectites such asmontmorillonite or hectorite.

Furthermore, it has proven to be advantageous when the coloring agents,in particular when they additionally include hydrogen peroxide, includeat least one stabilizer or complexing agent. Particularly preferredstabilizers are phenacetin, alkali benzoates (sodium benzoate), andsalicylic acid. In addition, all complexing agents of the prior art maybe used. Complexing agents preferred according to the invention arenitrogen-including polycarboxylic acids, in particular EDTA and EDDS,and phosphonates, in particular 1-hydroxyethane-1, 1-diphosphonate(HEDP) and/or ethylenediamine tetramethylene phosphonate (EDTMP) and/ordiethylenetriamine pentamethylene phosphonate (DTPMP) or the sodiumsalts thereof.

In addition, the agents according to the invention may include furtheractive substances, auxiliary substances, and additives, for examplenonionic polymers such as vinylpyrrolidinone/vinyl acrylate copolymers,polyvinylpyrrolidinone, vinylpyrrolidinone/vinyl acetate copolymers,polyethylene glycols and polysiloxanes; additional silicones such asvolatile or nonvolatile, straight-chain, branched, or cyclic,crosslinked or noncrosslinked polyalkylsiloxanes (such as dimethiconesor cyclomethicones), polyarylsiloxanes and/or polyalkylarylsiloxanes, inparticular polysiloxanes having organofunctional groups, such assubstituted or unsubstituted amines (amodimethicones), carboxyl, alkoxy,and/or hydroxyl groups (dimethicone copolyols), linear polysiloxane(A)-polyoxyalkylene (B) block copolymers, grafted silicone polymers;cationic polymers such as quaternized cellulose ethers, polysiloxaneshaving quaternary groups, dimethyldiallyl ammonium chloride polymers,acrylamide dimethyldiallyl ammonium chloride copolymers,dimethylaminoethyl methacrylate-vinylpyrrolidinone copolymersquaternized with diethyl sulfate, vinylpyrrolidinone-imidazoliniummethochloride copolymers, and quaternized polyvinyl alcohol;zwitterionic and amphoteric polymers; anionic polymers, for examplepolyacrylic acids or crosslinked polyacrylic acids; structurizers suchas glucose, maleic acid, and lactic acid, hair conditioning compoundssuch as phospholipids, for example lecithin and cephalins; fragranceoils, dimethyl isosorbide, and cyclodextrins; fiber structure-improvingactive substances, in particular mono-, di-, and oligosaccharides suchas glucose, galactose, fructose, fruit sugar, and lactose; dyes forcoloring the agent; anti-dandruff active substances such as piroctoneolamine, zinc omadine, and climbazole; amino acids and oligopeptides;animal- and/or plant-based protein hydrolysates, and in the form oftheir fatty acid condensation products or optionally anionically orcationically modified derivatives; plant oils; light protection agentsand UV blockers; active substances such as panthenol, pantothenic acid,pantolactone, allantoin, pyrrolidinone carboxylic acids and the saltsthereof, and bisabolol; polyphenols, in particular hydroxycinnamicacids, 6,7-dihydroxycoumarin, hydroxybenzoic acids, catechins, tannins,leucoanthocyanidins, anthocyanidins, flavanones, flavones, andflavonols; ceramides or pseudoceramides; vitamins, provitamins, andvitamin precursors; plant extracts; fats and waxes such as fattyalcohols, beeswax, montan wax, and paraffins; swelling agents andpenetration agents such as glycerin, propylene glycol monoethyl ether,carbonates, hydrogen carbonates, guanidines, ureas, and primary,secondary, and tertiary phosphates; opacifiers such as latex,styrene/PVP and styrene/acrylamide copolymers; pearlescence agents suchas ethylene glycol mono- and distearate and PEG-3-distearate; pigments,and propellants such as propane-butane mixtures, N₂O, dimethyl ether,CO₂, and air.

Those skilled in the art will select these further substances accordingto the desired properties of the agents. With regard to further optionalcomponents and the quantities of these components used, explicitreference is made to relevant handbooks known to those skilled in theart. The additional active substances and auxiliary substances arepreferably used in the agents according to the invention in each case inquantities of 0.0001 to 25% by weight, in particular 0.0005 to 15% byweight, in each case based on the total weight of the color preparation(K1) and/or the oxidizing agent preparation (K2).

The agents according to the invention show extremely good suitabilityfor dyeing keratinous fibers; the dyed fibers have very good washfastness and very good light fastness.

A further subject matter of the present invention therefore relates tothe use of an agent of the first subject matter of the invention forimproving the light fastness of the colorings obtained with this agent.

A further subject matter of the present invention relates to the use ofan agent of the second subject matter of the invention for improving thelight fastness of the colorings obtained with this agent.

A further subject matter of the present invention therefore relates tothe use of an agent of the first subject matter of the invention forimproving the wash fastness of the colorings obtained with this agent.

A further subject matter of the present invention relates to the use ofan agent of the second subject matter of the invention for improving thewash fastness of the colorings obtained with this agent.

The statements concerning the agents according to the invention applymutatis mutandis with regard to further embodiments of the kit accordingto the invention and the uses according to the invention.

EXAMPLES

1. Test Series 1

1.1. Production of the Coloring Agents

The following color creams were produced:

Color cream (quantity: 100 g) V1 V2 E1 (comparison) (comparison)(invention) 4,5-Diamino-1-(2-hydroxy- 4.80 g 4.80 g ethyl)-1H-pyrazole(sulfate) 20 mmol 20 mmol p-Aminophenol 1.46 g 4.37 g 1.46 g(hydrochloride) 10 mmol 30 mmol 10 mmol 2,6-bis(2′-Hydroxy- 8.41 g 4.21g 4.21 g ethylamino)-1-methylbenzene 40 mmol 20 mmol 20 mmol5-Amino-2-methylphenol — 2.46 g 2.46 g 20 mmol 20 mmol Hydrenol D(cetearyl alcohol) 8.5 g 8.5 g 8.5 g Technical Lorol (C12-C18 2.0 g 2.0g 2.0 g fatty alcohols) Texapon NSO (sodium laureth 20.0 g 20.0 g 20.0 gsulfate, approx. 27.5% by weight active substance) Dehyton K(cocoamidopropyl 12.5 g 12.5 g 12.5 g betaine, approx. 30% by weightactive substance) Sodium sulfite 1.0 g 1.0 g 1.0 g Ammonium sulfate 1.0g 1.0 g 1.0 g Water (distilled) ad 100 g ad 100 g ad 100 g

The color creams V1, V2, and E1 were in each case mixed in a 1:1 weightratio with the following oxidizing agent preparation.

Oxidizing agent preparation (quantity: 100 g) OX Dipicolinic acid 0.1 gSodium pyrophosphate 0.03 g Turpinal SL(1-hydroxyethane-1,1-diphosphonic acid, 1.50 g 58-61% by weight activesubstance) Texapon N28 (sodium laureth sulfate, at least 26.5% by 2.00 gweight active substance) Aerysol 22 (Acrylates/Steareth-20 Methacrylate0.60 g Copolymer, active substance 29.5-30.5% by weight) Hydrogenperoxide (50% aqueous solution) 6.0 g Sodium hydroxide solution (45%aqueous solution) 0.80 g Water (distilled) ad 100 gThe pH was set to 10.0 by adding a 25% aqueous ammonia solution.

1.2. Application

The ready-to-apply oxidative coloring agents (V1+OX, V2+OX, E1+OX)produced in this way were each applied to three hair strands (Kerling,Euronaturhaar white) and allowed to act for a period of 30 minutes atroom temperature. The strands were then rinsed with lukewarm tap waterfor one minute and dried in a cold air stream.

Each hair strand was subsequently colorimetrically measured at fourdifferent points in each case (two on the front side of the strand, twoon the rear side of the strand). The average was formed from the fourmeasured values.

1.3. Determination of Wash Fastness

To determine the wash resistance, a 2% standard shampoo solution wasfilled to the top fill mark in an ultrasonic bath. The hair strands tobe treated were completely immersed therein and treated with ultrasound.After a period of time corresponding to the equivalent of 12 repeatedmanual hair washings, the strands were removed from the ultrasonic bathand dried in a cold air stream.

Each hair strand was subsequently once again colorimetrically measuredat four different points in each case (two on the front side of thestrand, two on the rear side of the strand). The average was formed fromthe four measured values.

Based on the obtained L*a*b* values, in each case the color difference(ΔE value) between the unwashed strands and the strands washed in adefined manner was determined, using the CIELAB2000 formula. The ΔEvalues were used for determining the wash fastness; the larger the ΔEvalues in question, the lower the wash fastness rating. Eachready-to-apply oxidative coloring agent was intensely colored on threestrands.

The following ΔE values were obtained:

Wash Fastness after 12 Hair Washings

V1 + OX V2 + OX E1 + OX ΔE value 6.78 10.51 3.29

The hair strands treated with the oxidative coloring agent according tothe invention (E1+OX) showed a smaller ΔE value, and thus, improved washfastness, compared to the comparative formulations (V1+OX and V2+OX).

2. Test Series 2

2.1. Production of the Coloring Agents

The following color creams were produced:

The following color creams were produced V3 V4 E2 (comparison)(comparison) (Invention) 4,5-Diamino-1-(2-hydroxy- — 4.80 g 4.80 gethyl)-1H-pyrazole (sulfate) 20 mmol 20 mmol p-Aminophenol 4.38 g 1.46 g1.46 g (hydrochloride) 30 mmol 10 mmol 10 mmol2-(2,4-Diaminophenoxy)etha- 4.82 g — 4.82 g nol (dihydrochloride) 20mmol 20 mmol 5-Amino-2-methylphenol 2.46 g 4.94 g 2.46 g 20 mmol 40 mmol20 mmol Hydrenol D (cetearyl alcohol) 8.5 g 8.5 g 8.5 g Technical Lorol(C12-C18 2.0 g 2.0 g 2.0 g fatty alcohols) Texapon NSO (sodium laureth20.0 g 20.0 g 20.0 g sulfate, approx. 27.5% by weight active substance)Dehyton K (cocoamidopropyl 12.5 g 12.5 g 12.5 g betaine, approx. 30% byweight active substance) Sodium sulfite 1.0 g 1.0 g 1.0 g Ammoniumsulfate 1.0 g 1.0 g 1.0 g Water (distilled) ad 100 g ad 100 g ad 100 g

The color creams V3, V4, and E2 were in each case mixed in a 1:1 weightratio with the following oxidizing agent preparation.

Oxidizing agent preparation (quantity: 100 g) OX Dipicolinic acid 0.1 gSodium pyrophosphate 0.03 g Turpinal SL(1-hydroxyethane-1,1-diphosphonic acid, 1.50 g 58-61% by weight activesubstance) Texapon N28 (sodium laureth sulfate, at least 26.5% by 2.00 gweight active substance) Aerysol 22 (Acrylates/Steareth-20 Methacrylate0.60 g Copolymer, active substance 29.5-30.5% by weight) Hydrogenperoxide (50% aqueous solution) 6.0 g Sodium hydroxide solution (45%aqueous solution) 0.80 g Water (distilled) ad 100 aThe pH was set to 10.0 by adding a 25% aqueous ammonia solution.

2.2. Application

The application of the ready-to-apply oxidative coloring agents (V3+OX,V4+OX, and E2+OX) was carried out analogously to the applicationdescribed under Item 1.2.

2.3. Determination of Light Fastness

After the dyeing and colorimetric measurement, the dried strands wereclamped in metal holders and then placed in a UV weathering testapparatus. The strands were then irradiated in a defined manner with UVlight for a period of 98 hours (50 W/m²). The strands were subsequentlyremoved from the measuring device and colorimetrically measured onceagain.

Based on the obtained L*a*b* values, in each case the color difference(ΔE value) between the unexposed strands and the strands exposed in adefined manner was determined, using the CIELAB2000 formula. The ΔEvalues were used for determining the light fastness; the larger the ΔEvalues in question, the lower the light fastness rating.

The following ΔE values were obtained:

Light Fastness after an Exposure Period of 98 Hours

V3 + OX V4 + OX E2 + OX ΔE value 8.31 7.06 2.49

The hair strands treated with the oxidative coloring agent according tothe invention (E2+OX) showed a smaller ΔE value, and thus, improvedlight fastness, compared to the comparative formulations (V3+OX andV4+OX).

While at least one exemplary embodiment has been presented in theforegoing detailed description of the invention, it should beappreciated that a vast number of variations exist. It should also beappreciated that the exemplary embodiment or exemplary embodiments areonly examples, and are not intended to limit the scope, applicability,or configuration of the invention in any way. Rather, the foregoingdetailed description will provide those skilled in the art with aconvenient road map for implementing an exemplary embodiment of theinvention, it being understood that various changes may be made in thefunction and arrangement of elements described in an exemplaryembodiment without departing from the scope of the invention as setforth in the appended claims and their legal equivalents.

What is claimed is:
 1. An agent for oxidatively dyeing keratinousfibers, including in a cosmetic carrier (A)4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole and/or one of thephysiologically acceptable salts thereof as developer, (B) at least onep-aminophenol derivative selected from the group consisting ofp-aminophenol, 4-amino-3-methylphenol, and the physiologicallyacceptable salts of such p-aminophenol derivatives as developer, (C) atleast one m-diaminobenzene derivative selected from the group consistingof 2-(2,4-diamino-phenoxy)ethanol and one of the physiologicallyacceptable salts thereof as coupler, and (D) at least one m-aminophenolderivative selected from the group consisting of 5-amino-2-methylphenol,and one of the physiologically acceptable salts thereof as coupler,wherein a molar ratio (A)/(B) defined as the molar ratio of alldevelopers of group (A) included in the agent to all developers of group(B) included in the agent has a value of at least 1.2, and wherein amolar ratio (C)/(D), defined as the molar ratio of all couplers of group(C) included in the agent to all couplers of group (D) included in theagent has a value of at least 0.5 and has a maximum value of 1.5.
 2. Theagent according to claim 1, wherein the molar ratio (A)/(B), has a valueof at least 1.4.
 3. The agent according to claim 2, wherein the molarratio (A)/(B) has a maximum value of 4.5.
 4. The agent according toclaim 1, wherein the agent includes (B) 4-amino-3-methylphenol and/orone of the physiologically acceptable salts thereof as developer.
 5. Theagent according to claim 1, wherein the agent includes (B) p-aminophenoland/or one of the physiologically acceptable salts thereof as developer.6. The agent according to claim 1, wherein a molar ratio[(A)+(B)]/[(C)+(D)] defined as the ratio of all developers of groups (A)and (B) included in the agent to all couplers of groups (C) and (D)included in the agent has a value of at least 0.4.
 7. The agentaccording to claim 6, wherein the molar ratio [(A)+(B)]/[(C)+(D)] has amaximum value of 0.95 maximum.
 8. The agent according to claim 1,wherein the agent includes the developer(s) of group (A) in an overallmolality of 0.10 to 0.50 mol/kg based on the total weight of the agent.9. The agent according to claim 1, wherein the agent includes thecouplers of groups (C) and (D) in an overall molality of 0.10 to 1.00mol/kg based on the total weight of the agent.
 10. A multicomponentpackaging unit (kit-of-parts) for oxidatively dyeing keratinous fibers,comprising two preparations (K1) and (K2) that are separately packaged,wherein preparation (K1) is an agent according to claim 1, preparation(K2) includes hydrogen peroxide in an aqueous cosmetic carrier, and themixture of (K1) and (K2) has a pH of 8.0 to 10.5.